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Enhancing the Effectiveness of Oxygen Evolution Reaction by Electrodeposition of Transition Metal Nanoparticles on Nickel Foam Material

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Enhancing the Effectiveness of Oxygen Evolution Reaction by Electrodeposition of Transition Metal Nanoparticles on Nickel Foam Material catalysts Article Enhancing the Effectiveness of Oxygen Evolution Reaction by Electrodeposition of Transition Metal Nanoparticles on Nickel Foam Material Mateusz Łuba 1 , Tomasz Mikołajczyk 1,* , Mateusz Kuczy ´nski 1, Bogusław Pierozy˙ ´nski 1,* and Ireneusz M. Kowalski 2 1 Department of Chemistry, Faculty of Agriculture and Forestry, University of Warmia and Mazury in Olsztyn, Plac Lodzki 4, 10-727 Olsztyn, Poland; [email protected] (M.Ł.); [email protected] (M.K.) 2 Department of Rehabilitation, Faculty of Medical Sciences, University of Warmia and Mazury in Olsztyn, Zolnierska 14C Street, 10-561 Olsztyn, Poland; [email protected] * Correspondence: [email protected] (T.M.); [email protected] (B.P.); Tel.: +48-89-523-4177 (B.P.) Abstract: Electrochemical oxygen evolution reaction (OER) activity was studied on nickel foam-based electrodes. The OER was investigated in 0.1 M NaOH solution at room temperature on as-received and Co- or Mo-modified Ni foam anodes. Corresponding values of charge-transfer resistance, exchange current-density for the OER and other electrochemical parameters for the examined Ni foam composites were recorded. The electrodeposition of Co or Mo on Ni foam base-materials resulted in a significant enhancement of the OER electrocatalytic activity. The quality and extent Citation: Łuba, M.; Mikołajczyk, T.; of Co, and Mo electrodeposition on Ni foam were characterized by means of scanning electron Kuczy´nski,M.; Pierozy´nski,B.;˙ microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) analysis. Kowalski, I.M. Enhancing the Effectiveness of Oxygen Evolution Keywords: oxygen evolution reaction; Ni foam; Co-modified Ni foam; Mo-modified Ni foam; Reaction by Electrodeposition of electrodeposition; electrochemical impedance spectroscopy Transition Metal Nanoparticles on Nickel Foam Material. Catalysts 2021, 11, 468. https://doi.org/10.3390/ catal11040468 1. Introduction In recent years, the development of renewable energy sources has dramatically in- Academic Editor: Yongjun Feng creased [1,2], resulting from both a gradual depletion of crude oil sources, as well as progressive degradation of the natural environment [3,4]. Unfortunately, currently-used Received: 14 March 2021 green energy technologies are strongly dependent on weather conditions and topography. Accepted: 1 April 2021 Published: 3 April 2021 For instance, the energy production of solar panels reaches its peak value at noon; however, it does not meet the demands of energy consumption [5]. This phenomenon is well-known Publisher’s Note: MDPI stays neutral under the name of solar energy’s duck curve. Appropriate storage of this energy excess with regard to jurisdictional claims in could be the only solution to the above problem [6]. Currently, most of the produced published maps and institutional affil- renewable energy is stored in lithium-ion battery systems, because of their high-efficiency iations. and convenience in exploitation. However, all batteries have their limitations, such as slow charge and discharge time, which is strongly dependent on ambient temperature, as well as limited operational lifetime. Moreover, used batteries could become environmentally important hazardous waste. One of the most promising new energy storage technologies is based on hydrogen generation by means of alkaline water electrolysis (AWE) [7,8]. Such Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. produced hydrogen can be considered an entirely environmentally friendly energy carrier, This article is an open access article since the only by-products generated during the hydrogen combustion are heat and water distributed under the terms and (see Equation (1)) [9]. conditions of the Creative Commons 2H2 + O2 ! 2H2O + Q (1) Attribution (CC BY) license (https:// While many catalysts are known to reduce the overpotential of hydrogen evolution creativecommons.org/licenses/by/ reaction (HER), the more complex oxygen evolution (OER) process still requires a large 4.0/). Catalysts 2021, 11, 468. https://doi.org/10.3390/catal11040468 https://www.mdpi.com/journal/catalysts Catalysts 2021, 11, 468 2 of 13 amount of energy to proceed. Contrary to a comparatively fast single-electron transfer cathodic process, the OER is related to a slow and complex, four-electron transfer reaction (see Equation (2)) [10,11]. − − 4OH ! O2 + 2H2O + 4e (2) Hence, in order to minimize the overpotential of the OER, the researchers have made significant efforts in developing new types of anodes. As a result, electrodes based on ruthenium [12] and iridium [13] oxides were found to exhibit outstanding electrochem- ical properties towards the OER; however, because of their high costs, the use of these materials on the industrial scale is not economically practical. Therefore, in recent years, the researchers’ attention has been shifted to more abundant and inexpensive transitional metals (Ni, Co, Mn, Mo, Fe) [14–16] and their alloys [17], oxides and carbides [18,19] to replace platinum group metals. Thus, one of the most commonly used base materials to make electrodes, in the hydrogen production industry, are nickel and its derivatives. The employment of nickel and nickel-coated electrodes results from their unique properties, such as high catalytic activity in both hydrogen and oxygen evolution reactions. In addition, nickel exhibits superior anticorrosion properties in an alkaline environment. Generally, it is well-known that the OER on metals proceeds on the surface covered by their oxides, where nickel oxide/hydroxide species are especially catalytic in this reaction [20–26]. However, in order to compete with the electrocatalytic properties of electrodes based on noble metals, newly developed electrodes have to be characterized by large and highly active surface areas (HASA). Large values of HASA could be easily achieved by employing various materials, including foams, fibres, nanowires or nanocones. Such a base material could then be modified with a trace amount of transition metal(s) by one of the deposition methods (electrochemical, electroless, CVD: chemical vapour deposition or PVD: physical vapour deposition), which could further enhance the electrocatalytic properties of these innovative materials [20,21]. Nickel foam could be considered one of the most promising candidates for fabricating such a highly reactive anode in the process of the OER, as in addition to its unique electrocatalytic properties, Ni foam also provides large values of HASA. Nickel is also relatively inexpensive, compared to most noble metals [22]. In this work, electrochemically modified Ni foam materials were assessed as potential anodes towards the OER in alkaline 0.1 M NaOH environment through the employment of major electrochemical techniques. In addition, the structure and quality of electrodeposited Co and Mo on the surface of nickel foam were evaluated by means of a combined scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) methodology. 2. Results and Discussion 2.1. SEM/EDX Characterization of Ni Foam and Co-, and Mo-Modified Nickel Foam Electrodes Figure1a,b below illustrate SEM micrograph pictures of the electrodeposition effect of Co and Mo at small and trace amounts, respectively, on the Ni foam surface, recorded at the same magnification level. For the Co-modified Ni foam (at ca. 1 wt.% Co), the surface of the base material is densely covered with a granular structure of small Co nuclei (see Figure1a). On the other hand, a sample of Mo-modified Ni foam (at ca. 0.2 wt.% Mo) is comparatively shown in a SEM micrograph picture of Figure1b. The electrodeposited sample is covered with quite an irregular, amorphous and discontinuous structure through the Ni foam surface. In addition, the more detailed information on the composition of the prepared samples is shown in Table1. Moreover, Figure1c,d demonstrate the EDX pattern of Co- and Mo-modified Ni foam electrodes, respectively. In addition, the SEM-approximated Co and Mo grain size value came to 50.0 ± 3.5 and 512 ± 9.8 nm, respectively. The above was performed through utilization of the Image Analysis Program (NIS-Elements Basic Research on Nikon). Catalysts 2021, 11, x FOR PEER REVIEW 3 of 13 Catalysts 2021, 11, 468 3 of 13 shown in Table 1. Moreover, Figure 1c,d demonstrate the EDX pattern of Co- and Mo- modified Ni foam electrodes, respectively. Figure 1. SEM micrograph pictures of Co-modified Ni foam surface (a), and Mo-activated Ni foam surface (b), taken at 5000× magnificationFigure 1. withSEM EDXmicrograph pattern ofpictures Co- (c )of and Co-modified Mo-activated Ni foam (d) Ni surface foam samples. (a), and Mo-activated Ni foam surface (b), taken at × 5000 magnification with EDX pattern of Co- (c) and Mo-activated (d) Ni foam samples. Catalysts 2021, 11, x FOR PEER REVIEW 4 of 13 Table 1. EDX-derived (for an acceleration voltage of 15 kV) chemical composition of surface elements for freshly prepared: Co- and Mo-modified Ni foam samples. Catalysts 2021, 11, 468 4 of 13 Element/% Spectrum 1 Spectrum 2 Co-modified Ni foam Ni 95.83 92.84 Co 1.06 1.25 Table 1. EDX-derived (for an acceleration voltage of 15 kV) chemical composition of surface elements O 3.11 5.91 for freshly prepared: Co- and Mo-modified Ni foam samples. Total: 100.00 100.00 Mo-modified Ni foam Element/%Ni Spectrum92.08 1 Spectrum86.42 2 Co-modified Ni foam NiMo 0.25 95.83 0.33 92.84 CoO 2.61 1.06 5.06 1.25 OC 5.06 3.11 8.19 5.91 Total: 100.00 100.00 Total: 100.00 100.00 Mo-modified Ni foam Ni 92.08 86.42 Mo 0.25 0.33 In addition, the SEM-approximated Co and Mo grain size value came to 50.0 ± 3.5 and O 2.61 5.06 512 ± 9.8 nm, respectively. The Cabove was performed 5.06 through utilization 8.19of the Image Analysis Program (NIS-ElementsTotal: Basic Research on 100.00Nikon). 100.00 2.2.2.2.
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